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Ultrafast lattice disordering can be accelerated by electronic collisional forces

Nature Physics volume 19, pages 1489–1494 (2023)Cite this article

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Abstract

In the prevalent picture of ultrafast structural phase transitions, atomic motion occurs in a slowly varying potential energy surface adiabatically determined by fast electrons. However, this ignores non-conservative forces caused by electron–lattice collisions, which can substantially influence atomic motion. Most ultrafast techniques only probe the average structure and are less sensitive to random displacements and therefore do not detect the role played by non-conservative forces in phase transitions. Here we show that the lattice dynamics of the prototypical insulator–metal transition of vanadium dioxide cannot be described by potential energy alone. We use the sample temperature to control the preexisting lattice disorder before ultrafast photoexcitation across the phase transition and our ultrafast diffuse scattering experiments show that the fluctuations characteristic of rutile metal develop equally fast (120 fs) at initial temperatures of 100 and 300 K. This indicates that additional non-conservative forces are responsible for the increased lattice disorder. These results highlight the need for more sophisticated descriptions of ultrafast phenomena beyond the Born–Oppenheimer approximation as well as ultrafast probes of spatial fluctuations beyond the average unit cell measured by diffraction.

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Fig. 1: Effect of non-conservative electronic forces on structural dynamics.
Fig. 2: Ultrafast X-ray diffraction and diffuse scattering from VO2.
Fig. 3: Influence of the initial temperature on the dynamics.
Fig. 4: Model of disorder with non-conservative forces.

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Data availability

Source data are available with this paper. Other data that support the findings of this study are available from the corresponding authors upon reasonable request.

Code availability

Computer codes used in this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

G.A.d.l.P.M., Y.H., V.K., D.A.R., S.T. and M.T. were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, through the Division of Materials Sciences and Engineering under contract no. DE-AC02-76SF00515. A.A.C. was supported by the Center for Non-Perturbative Studies of Functional Materials Under Non-Equilibrium Conditions (NPNEQ) funded by the Computational Materials Sciences Program of the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, and performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344. O.D. was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division, under award no. DE-SC0019978. A.S.J., E.P., L.V. and S.W. were funded through the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme (grant agreement no. 758461) and PGC2018-097027-B-I00 project funded by MCIN/AEI/10.13039/501100011033/FEDER ‘A way to make Europe’ and CEX2019-000910-S (MCIN/AEI/10.13039/501100011033), Fundació Cellex, Fundació Mir-Puig and Generalitat de Catalunya (AGAUR grant no. 2017 SGR 1341, CERCA program). A.S.J. and E.P. acknowledge support from the Marie Skłodowska-Curie grant agreement no. 754510 (PROBIST). A.S.J. acknowledges support of a fellowship from ‘la Caixa’ Foundation (ID 100010434), fellowship code LCF/BQ/PR21/11840013, and the Agencia Estatal de Investigacion (the R&D project CEX2019-000910-S, funded by MCIN/AEI/10.13039/501100011033, Plan National FIDEUA PID2019-106901GB-I00, FPI). T.K. acknowledges support from JSPS KAKENHI (grant nos. JP19H05782, JP21H04974 and JP21K18944). Ultrafast X-ray measurements were performed at BL3 of SACLA with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal nos. 2019A8038 and 2019B8075). Preliminary X-ray characterization was performed at the Stanford Synchrotron Radiation Lightsource (SSRL). Use of the SSRL is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-76SF00515.

Author information

Authors and Affiliations

  1. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Gilberto A. de la Peña Muñoz, Yijing Huang, Viktor Krapivin, David A. Reis & Mariano Trigo

  2. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Gilberto A. de la Peña Muñoz, Yijing Huang, Viktor Krapivin, David A. Reis & Mariano Trigo

  3. Quantum Simulations Group, Lawrence Livermore National Laboratory, Livermore, CA, USA

    Alfredo A. Correa

  4. Department of Mechanical Engineering and Materials Science, Duke University, Durham, NC, USA

    Shan Yang & Olivier Delaire

  5. ICFO–Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, Castelldefels, Spain

    Allan S. Johnson, Ernest Pastor & Luciana Vidas

  6. IMDEA Nanoscience, Madrid, Spain

    Allan S. Johnson

  7. Japan Synchrotron Radiation Research Institute, Sayo-cho, Sayo-gun, Japan

    Tetsuo Katayama

  8. RIKEN SPring-8 Center, Sayo, Japan

    Tetsuo Katayama

  9. IPR–Institut de Physique de Rennes, CNRS–Centre national de la recherche scientifique, UMR 6251 Université de Rennes, Rennes, France

    Ernest Pastor

  10. Physics Department, Arizona State University, Phoenix, AZ, USA

    Samuel Teitelbaum

  11. Department of Physics and Astronomy, Aarhus University, Aarhus, Denmark

    Simon Wall

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  1. Gilberto A. de la Peña Muñoz
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Contributions

M.T., S.W. and O.D. conceived the initial experiment. M.T. supervised the project. G.A.d.l.P.M., Y.H., A.S.J., T.K., V.K., E.P., D.A.R., S.T., L.V., S.W. and M.T. performed the experiment at SACLA. G.A.d.l.P.M. analysed the data. M.T. and A.A.C. developed the model, and M.T., G.A.d.l.P.M. and S.Y. performed the simulations. M.T. and A.A.C. wrote the initial draft with feedback from all the authors.

Corresponding authors

Correspondence to Alfredo A. Correa or Mariano Trigo.

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Nature Physics thanks Jorgen Larsson, Christoph Rau and Michael Sentef for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Ab-inito molecular dynamics.

Ab-inito molecular dynamics (AIMD) of the disordering process after the electronic temperature is raised to 2200 K and kept fixed (see10 for details of the simulation). The plot shows the V-V distance as a function of time for multiple MD trajectories (black lines). Blue and red lines show the long and short bonds averaged over multiple unit cells. The lattice is initially at 300 (top) and 100 K (bottom). Note that this simulation is done under the Born-Oppenheimer approximation. The trajectories disorder faster starting at 300 K than when starting at 100 K.

Extended Data Fig. 2 Additional X-ray diffuse patterns.

Static x-rays scattering pattern at 100K with Brillouin zone boundaries shown for the VO2 M1 and M1’ domains, a) and b) respectively. Monoclinic Miller indices for each Brillouin zone are indicated. The M1’ domain is rotated by 90 degrees around the rutile c-axis from the M1 domain.

Extended Data Fig. 3 Fits of the time dependence.

Dashed lines are fits of an error function, Erf((t - μ)/σ), to the time dependent intensities of the Bragg and diffuse regions at 100K (left column) and 300K (right column) shown in Fig. 3 of the main text. The fitted μ and σ are given on the legend. The timescales quoted in the main text correspond to the full width at half maximum equivalent, FWHM = \(2\sqrt{2\ln (2)}\sigma\).

Source data

Source Data Fig. 2

Source data for the integrated intensity as a function of time for Bragg peaks (–122) and (–113) and for diffuse regions Q1 and Q2.

Source Data Fig. 3

Source data for the curves in Fig. 3.

Source Data Fig. 4

Tabulated values for the data plotted in Fig. 4f,g. The columns represent the temperatures (T = 0.002, 0.005, 0.010, 0.015) as described in the main text.

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de la Peña Muñoz, G.A., Correa, A.A., Yang, S. et al. Ultrafast lattice disordering can be accelerated by electronic collisional forces. Nat. Phys. 19, 1489–1494 (2023). https://doi.org/10.1038/s41567-023-02118-z

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